Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
  • B01J27/051—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
  • B01J27/04—Sulfides
  • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
  • B01J27/051—Molybdenum
  • B01J27/0515—Molybdenum with iron group metals or platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0027—Powdering
  • B01J37/0045—Drying a slurry, e.g. spray drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/033—Using Hydrolysis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G51/00—Compounds of cobalt
  • C01G51/30—Sulfides

Definitions

• This invention relates to preparation of catalysts such as those that are frequently employed to convert synthesis gas to an alcohol. More particularly, this invention relates to an improved process to dry the precipitated catalyst precursor attained during production of such catalysts to form a free-flowing particulate catalyst precursor having a reduced propensity for oxidation and self-heating on exposure to air, which would lead to decreased catalyst activity and selectivity to desired alcohols.
• Catalysts including molybdenum, sulfur and, optionally, cobalt have been found to be useful to convert synthesis gas to an alcohol.
• Synthesis gas is a mixture of carbon monoxide and hydrogen and is one of the most readily available starting materials for production of alcohols. These alcohols may include, in non-limiting example, ethanol and propanol.
• the molybdenum sulfide-based catalysts have been found to be very important in increasing both the alcohol production rate and yield, but processes to produce the catalysts themselves at large scale (metric tons and above) have often faced problems. These problems include, in many cases, a wet filter cake that is difficult to handle and/or dried catalyst precursor that may undergo oxidation and self-heating which leads to a decline in activity.
• compositions for catalyzing the conversion of syngas into products comprising at least one C1-C4 alcohol, such as ethanol.
• These compositions generally include cobalt, molybdenum, and sulfur, and avoid metal carbides both initially and during reactor operation.
• EP0216472 A1 discloses an attrition-resistant, unsupported catalytic sulfide containing Nb, Ta, Mo, W, Tc, or Re, used for preparing C1-10 aliphatic hydrocarbons or C1-10 mixed alcohols from synthesis gas.
• the catalytic sulfide is prepared by precipitating a centric particulate precursor, preferably (NH 4 ) 2 MoS 2 O 2 , and then thermally decomposing the precursor.
• the catalytic sulfide can optionally have a metal promotor.
• the present invention is directed to a process for preparing a molybdenum sulfide-based catalyst comprising drying a precipitated molybdenum sulfide-based catalyst precursor containing at least molybdenum and sulfur, under conditions such that a particulate catalyst precursor containing from 12 to 15 percent by weight water is formed;
• the invention provides a preparation process for a molybdenum sulfide-based catalyst wherein a moisture content and other conditions under which the catalyst's precipitated precursor may be transformed to particles and, in particularly preferred embodiments, to free-flowing particles. It also facilitates further processing to prepare the final catalyst that may be suitable for practice on a commercial scale.
• molybdenum sulfide-based refers to catalyst(s) or catalyst precursor(s) containing at least molybdenum and sulfur, but which may also contain additional metals including, but not limited to, cobalt, nickel, iron, chromium, manganese, tungsten, vanadium and zirconium.
• the precipitated catalyst precursor is the molybdenum sulfide-based reaction product which has been isolated from the reaction mixture, but not yet subjected to any further processing.
• This precipitated catalyst precursor may be prepared by a reaction of, for example, ammonium tetrathiomolybdate and cobalt acetate; ammonium heptamolybdate, ammonium hydrosulfide and cobalt acetate; or ammonium helptamolybdate and ammonium sulfide. Examples of suitable methodology to prepare the precipitated catalyst precursor are discussed in, for example, USP 4,825,013 , which is incorporated herein by reference in its entirety.
• the precipitated catalyst precursor is subjected to either a combination of vacuum drying and pressure filtration, using, for example, a diaphragm or membrane filter, which results in formation of a so-called “wet filter cake,” or the precipitated catalyst precursor is used to form a slurry suspension which is then spray-dried.
• the vacuum dryer temperature desirably ranges from 30 degrees Celsius (°C) to 70 °C, more desirably from 39 °C to 47 °C, and dryer pressure ranges from 5 kilopascals (kPa) to 30 kPa, more desirably from 10 kPa to 15 kPa.
• Filtration pressures may range from 207 kPa to 620 kPa, desirably from 379 kPa to 517 kPa.
• Drying time may range from 30 minutes to 24 hours, desirably from 30 to 120 minutes. Drying in the vacuum dryer may be carried out under an inert atmosphere, for example, nitrogen, or alternatively employing an air feed.
• the air feed rate desirably ranges from 1 to 10 standard cubic feet per minute (scfm) (28.37 liters per minute (L/min) to 283.17 L/min) for a 100 liter (L) vacuum drier.
• scfm standard cubic feet per minute
• L/min liters per minute
• L/min 100 liter
• L vacuum drier
• An air feed rate in this range may accomplish passivation of the precipitated catalyst precursor. This passivation will help to reduce any potential self-heating that the precursor may subsequently experience prior to auto-reduction, which will, in turn, help to preserve future catalyst activity and selectivity.
• the initial concentration of the precipitated catalyst precursor may range from 10 percent by weight (wt%) to 40 wt% solids, but is desirably from 20 wt% to 35 wt% solids.
• the water content of the precipitated catalyst precursor is reduced to a level ranging from 12 wt% to 15 wt%, at which time it is desirably particulate and therefore referred to as the particulate catalyst precursor.
• the material is desirably in the form of free-flowing particles.
• the particles desirably exhibit an average size greater than (>) U.S. 40 mesh (0.400 millimeters (mm)), more desirably > U.S. 20 mesh (0.841 mm) and still more desirably > U.S. 10 mesh (2.00 mm).
• U.S. 230-80 mesh particles 63 micrometer ( ⁇ m)-177 um diameter particles
• the particulate catalyst precursor is passivated in a separate step, assuming such was not carried out during the drying step as previously described, by means of exposure to dilute air (having a concentration of > 0.1 percent by volume (vol%) and less than ( ⁇ ) 20 vol% oxygen), and subsequently auto-reduced.
• the auto-reduction is carried out by heating at a temperature ranging from 350 °C to 550 °C, more desirably from 450 °C to 550 °C, using any means known to those skilled in the art to be useful for this level of heating. Such may include, but is not limited to, a rotary furnace wherein an inert atmosphere can be established and maintained.
• the auto-reduction step results in removal of remaining water as well as production of a product having a reduced tendency, in comparison with the product of some other methods, to self-heat, which helps to preserve final catalytic activity.
• auto-reduction may be effectively and conveniently carried out in a rotary furnace.
• a rotary furnace may be effectively and conveniently carried out in a rotary furnace.
• a means such as a screw to move the precipitated catalyst precursor into and through the furnace, so that it undergoes auto-reduction to form a catalyst product.
• Such distinct temperature zones may include, in certain embodiments, a first temperature zone ranging from 150 °C to 400 °C and a second temperature zone ranging from 450 °C to 550 °C.
• the catalyst may then be mixed with an alkali metal promoter, a lubricant, and an optional clay binder material, in order to make formed catalyst bodies such as pellets or extrudates.
• the alkali metal promoter may be any alkali metal in free or combined form.
• the alkali metal promoter is potassium carbonate.
• the alkali metal promoter ranges in amount from 1 wt% to 20 wt%, based upon the combined weight of the three components and, if present, the optional clay binder material.
• the alkali metal promoter is from 5 wt% to 15 wt%, on the same basis.
• the alkali metal promoter may be simply dryblended with the molybdenum sulfide-based catalyst particles or the particles may be impregnated with the promoter from an aqueous or non-aqueous promoter solution.
• a lubricant such as a stearate, is desirably added at from 2 wt% to 6 wt%, frequently 4 wt%, based upon the combined weight of the three components and the clay binder material, to aid in pellet formation.
• the optional clay material is desirably in an amount ranging from 5 wt% to 30 wt%, on the same basis. In particular embodiments, the amount of clay binder material is from 15 wt% to 25 wt%, on the same basis.
• the drying and passivation conditions are the same as in Comparative Example B. Notice that the discharge valve feels very hot. Purge the valve with nitrogen and allow the valve to cool before discharging. Determine that, when the material in the dryer goes through the "tar" stage, some of it flows through the partially opened discharge valve and collects on top of the sparge plate. The passivation air causes the material in the area between the valve and the plate to oxidize. Because there is no mixing or cooling, the valve becomes very hot at this location.
• This procedure produces a desirably aggregated, non-sticky, flowable particulate catalyst precursor.
• the jacket oil temperature is set at 95 °C, which results in an actual jacket temperature, due to heat loss in the transfer lines, of 82 °C.
• the final product does not self-heat to a temperature above 50 °C and is in the form of free-flowing particles having a moisture content of from 12 wt% to 15 wt%.

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• 2011
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  • 2011-04-01 EP EP11713631.7A patent/EP2694207B1/en active Active
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